Substantive polyazo dyestuffs and their manufacture



. ,the type Patented Nov. 14, 1939 UNITED STA-res P TEN F r sUnsrAN'rIvEPOLYAZO .DYESTUFFS AND THEIR MANUFACTURE Adolf .Kreb s erLRiehen, nearBasel, Switzerland,

assignor to the firm of J. R.

Switzerland Geigy'A. G., Basel,

NJDrviiiil Q -glppilication April 14, 1938, Serial No. 202,127. InSwitzerland April 21, 1937 Claims.

This invention relates to of polyazo substantive dyestufis, and providesa process of producing valuable dyestuffs dyeing textile materialssuchas cotton 'a blue.

United States Patent No. 1,829,672 describes a process for theproduction of tetrakisazo dyestufis in which diaz ocompounds of disazodyestuffs of fast greeny- (wherein A represents the residue of a benzeneor naphthalene sulphonic or carboxylic acid and 7 ,,M1 and M2 are theresidues of l-naphthylamine l-naphthylamine-G- or -7-sulphonic acid or amixture of the two sulphonic acids) are combined with a monoazodyestufi' obtainable by coupling in acid solution a diazo body of thebenzene and naphthalene series with 2:5-aminonaphthol-7- "monosulphonicacid.

United StatesPatent No. 1,829,673 claims a process for the production ofsimilar dyestu'fis in which diazo compounds of disazddyestuffs of thegeneral formula wherein A and B represent the residues A'and M1 ofthe-Patent No. 1,829,672, but C represents the residue of a1:2-aminonaphtholether-6-sulphonic acid, are combined with acid coupledmonoazo dyestwfs of the 2:5-amino-naphtho1-7- monosulphonic acid in acidsolution.

According to the present invention :valuablefl light-fast dyestuifs ofgreeny-blue dyeing tone are obtained by combining diazo compounds ot(wherein A represents the residue of a benzene or naphthalenederivative, M1 the residue of 1- naphthylamine; 1-naphthy1amine-6- or7-su1} phonic acid or a mixture of the two sulphonic acids, but M2represents the residue of amino v hydroquinone-dialkylor-diaralkyl-ethers) with monoazo dyestufis which are obtained by cou-'pling in acid solution diazo compounds with 2:5-amino-naphthol--7-monosulphonic acid. 2

The use of these amino-hydr6q1iihone-dialliyl or -diaralkylethers islmhwn for the production of substantive azo dyestuffs, for example fordisazo dyestuffs in British Patent No. 15,403/1909 and fortrisazddyestufis in British specification 432,122 with amino-benZoyI-Z:5-amino-naphthol-7-monosulphonic acid as final component. Compared withthese known combinations the new tetraliis'azo dyestuffs of thepresentinvention are characte rise' d bya change of thedyeing tonetowardsfgreeny-blue and an improvement of the" fastness'to light. H IExample 17.3 parts or aniline-o-sulphonic acid aredi azotised andcoupled in known" manner with" 24=.5i

parts" of Cleves 1-'naphthy1amine 7 sulphonic 10 acid. Furtherdiazotisingis effected, the diazo bodyis isolated and coupled in aweakne-n acid'solution with 16 partsofamino-hydrodui;

none-dimethyl-ether. After completion of the coupling further.diazotising is effected and the new diazo compound is salted out andfiltered off.

The grey-black press-cakes are fcrmed intc paste with water at 0 C;andintroduced intoa solution, produced with 400 partsof'water and 30parts of, 20% ammonia,,of a monoazo dye stuff, which in turn is obtainedin known manner,

by acid combination of 17.3 parts of .diazo tised metanilic acid with 24parts of fzr5 amino naphthol-7-monosulphonic acid. After completion 012;

the coupling the bronzing dyestuff. isseparated completely with a littlesa1t,.filtered off and dried.

It dissolves blue in water, blue-grey in concen tratedsulphuric acid,and dyes cotton directly in fast. greeny-blue shades.

Instead of o-sulphanilicacid usedas initial component, there may beused, also in the place of diazotised metanilic acid, coupled in acidsolution with 2 5;amin o-naphthol-7-monosulphonic acid; any otherdiazotisable compounds of the benzfene or naphthalene series. Forexample ethylordiben'zyl-com'pound mayjbe'usedg. The] dyestuffs.obtained have. quite similar. properties;

As further examples thefollowing' dyestufis may be enumerated:Aniline-o-sulphonic acid-azo-lnaphthylamine-Z-sulphonicacid-azo-amino-hy- 'droquinone diethyl ether-azo-Z:5 aminonaphthol 7monosulphonic, acid azo 4 chloro-laminokfenzene-ii-sulphdnic acid orZ-naphthyl amine- 4:8 disulphonic acid-azo 1 naphthylamine-G- and-7-su1phonic acid-mixture-azoamino hydroquinone dimethylether azo -2 5-amino-naphthol-7-monosulphonic acid azo sulfanilio acid.

What I claim is:

1. A process for the manufacture of substantive polyazo-dyestuffscomprising coupling a diazocompound of a disazo-dyestufi of the typewherein A represents a member of the group consisting of residues ofbenzene and naphthalene sulphonic acids, M1 represents a member of thegroup consisting of residues of a-naphthylamine,1-naphthylamine-fi-sulphonic acid, l-naphthylamine-'I-sulphonic acid,and a mixture of 1- naphthylamine-6-sulphonic acid andl-naphthylamine-'l-sulphonic acid, and M2 represents a member of thegroup consisting of amino-hydroquinone-dialkylandamino-hydroquinone-diaralkyl-ethers, with a monoazo-dyestuff obtainableby coupling in acid solution a member of the group consisting ofdiazotized amino-sulphonic acids of the benzene and naphthalene serieswith 2 :5-amino-naphthol-7-monosulphonic acid.

2. A process for the manufacture of substantive polyazo-dyestuifscomprising coupling a diazo-compound from aniline-o-sulphonicacidazo-l-naphthylamine-l-sulphonicacid-azo-amino-hydroquinone-dimethylether with a monoazodyestuffobtainable by coupling in acid solution a member of the group consistingof diazotized amino-sulphonic acids of the benzene and naphthaleneseries with 2:5-aminonaphthol-7-monosulphonic acid.

3. A process for the manufacture of substantive polyazo-dyestufiscomprising coupling a diazo-compound of a disazo-dyestuff of the typewherein A represents a member of the group consisting of residues ofbenzene and naphthalene sulphonic acids, M1 represents a member of thegroup consisting of residues of m-naphthylamine,l-naphthylamine-6-sulphonic acid, 1naphthylamine-'I-sulphonic acid, anda mixture of l-naphthylamine-G-sulphonic acid andl-naphthylamine-'Z-sulphonic acid, and M2 represents a member of thegroup consisting of amino-hydroquinone-dialkylandamino-hydroquinone-diaralkyl-ethers, with a monoazo-dyestuff obtainableby coupling in acid solution a diazotized metaaminobenzene sulphonicacid with 2:5-aminonaphthol-7-monosulphonic acid.

4. A process for the manufacture of substantive polyazo-dyestuffscomprising coupling a diazo-compound from aniline-o-sulphonic acid- SOaHSOzH

azo-l-naphthylamine-T-sulphonicacid-azo-amino-hydroquinone-dimethylether with a monoazodyestufiobtainable by coupling in acid solution diazotized metanilic acid with2:5-aminonaphthol-7 -monosu1phonic acid.

5. A process for the manufacture of substantive polyazo-dyestuffscomprising coupling a diazo-compound from2-naphthylamine-4z8-disulphonic acid-azo-l-naphthyl-amine-6- and -'7-sulphonic acid mixture azo amino-hydroquinone-dimethylether with amonoazo-dyestuff obtainable by coupling in acid solution diazotizedsulfanilic acid with 2:5-aminonaphthol-7-monosulphonic acid.

6. A process for the manufacture of substantive polyazo-dyestufi'scomprising coupling a diazocompound from aniline-o-sulphonicacid-azo-lnaphthylamine-7-sulphonicacid-azo-amino-hydroquinone-diethylether with a monoazo-dyestuffobtainable by coupling in acid solution diazotized 4 chloro 1aminobenzene-3-sulphonic acid with 2:5-amino-naphthol-'7-monosulphonicacid.

7. The substantive polyazo-dyestuffs which correspond in the free stateto the following formula H038 NHz OCHa l :N M as O C H3 H0 SOaH 9. Thesubstantive polyazo-dyestufi which corresponds in the free state to thefollowing formula 10. The substantive polyazo-dyestufi which correspondsin the free state to the following formula.

HOaS- 0 OH; H0

. 10 N=NOsom QOaH

